title: Theoretical studies on the tautomerism and intramolecular hydrogen shifts of 5-amino-tetrazole in the gas phase.
abstract: The tautomerism and intramolecular hydrogen shifts of 5-amino-tetrazole in the gas phase were studied in the present work. The minimum energy path (MEP) information of 5-amino-tetrazole was obtained at the CCSD(T)/6-311G**//MP2/6-311G** level of theory. The six possible tautomers of 1H, 4H-5-imino-tetrazole (a), 1H-5-amino-tetrazole (b), 2H-5-amino-tetrazole (c), 1H, 2H-5-imino-tetrazole (d), the mesoionic form (e) and 2H, 4H-5-imino-tetrazole (f) were investigated. Among these tautomers, there are 2 amino- forms, 3 imino- forms, and 1 mesoionic structure form. In all the tautomers, 2-H form (c) is the energetically preferred one in the gas phase. In the imino- tautomers, the energy value of the compound d is similar as that of the compound f but it is higher than the energy value of the compound a. The potential energetic surface (PES) and kinetics for five reactions have been investigated. Reaction 2 (b-->c) was hydrogen shifts only in which the 1-H and 2-H rearrangement. This means that the reaction 2 (b-->c) is energetically favorable having an activation barrier of 45.66 kcal.mol(-1) and the reaction energies (DeltaE) is only 2.67 kcal.mol(-1). However, the reaction energy barrier for tautomerism of reaction 1 (b-->e) is 54.90 kcal.mol(-1). Reaction 1 (b-->a), reaction 3 (c-->d), and reaction 5 (c-->f) were amino- -->imino- tautomerism reactions. The energy barriers of amino- -->imino- tautomerism reactions required are 59.39, 65.57, 73.61 kcal.mol(-1) respectively in the gas phase. The calculated values of rate constants using TST, TST/Eckart, CVT, CVT/SCT and CVT/ZCT methods using the optimized geometries obtained at the MP2/6-311G** level of theory show the variational effects are small over the whole temperature range, while tunneling effects are big in the lower temperature range for all tautomerism reactions.
authors.affiliation: State Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology, Beijing 100081, People's Republic of China. zhangjianguobit@yahoo.com.cn
authors.forename: Jian-Guo
authors.initials: JG
authors.lastname: Zhang
authors.forename: Li-Na
authors.initials: LN
authors.lastname: Feng
authors.forename: Yuan-Jie
authors.initials: YJ
authors.lastname: Shu
authors.forename: Shao-Wen
authors.initials: SW
authors.lastname: Zhang
authors.forename: Tong-Lai
authors.initials: TL
authors.lastname: Zhang
authors.forename: Li
authors.initials: L
authors.lastname: Yang
authors.forename: Man
authors.initials: M
authors.lastname: Wu
mesh_terms: D005740:Gases / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D007536:Isomerism; D008958:Models, Molecular; D013777:Tetrazoles / Q000737:chemistry*; D013816:Thermodynamics
chemical_list: D005740:Gases; D013777:Tetrazoles; C001573:5-amino-1H-tetrazole; D006859:Hydrogen